Process for the preparation of branched olefins

Abstract: Process for the preparation of branched olefins comprising contacting a hydrocarbonaceous feedstock comprising linear olefins having at least four carbon atoms at elevated temperature with a catalyst which comprises a MeAPO and/or MeAPSO medium-pore molecular sieve having an anhydrous composition expressed in molar oxide ratios as follows; (MeO) a (Al₂O₃) b (P₂O₅) c (SiO₂) d , whereby (a + b)/c is greater than 1.0, a ranges from 0.003 to 0.2, b and c range from 0.05 to 0.3, d is at most 0.4 and a/(c + d) is at least 0.05 when SiO₂ is present, and Me is at least one of Mg, Mn, Co and Zn.

Description: The present invention relates to a process for the preparation of branched olefins from a hydrocarbonaceous feedstock comprising linear olefins having at least four carbon atoms. One of the main objects in nowaday's oil refining is to produce gasolines fulfilling the increasing environmental demands on product quality and having a high octane number. This means for gasoline that the octane specification has now to be established without lead-containing additives, less aromatics, in particular benzene, less olefins and lower gasoline vapour pressure. Components which are suitable for improving the octane quality of gasoline are certain highly branched ethers, e.g. methyl tertiary butyl ether (MTBE). It is known that such ethers can be formed by contacting branched olefins, e.g. branched butenes, with methanol in the presence of a suitable acidic catalyst, such as sulphonic resins, phosphoric acid, modified kieselguhr, silica/alumina and acidic zeolites. A process for preparing branched butenes has for instance been described in US 5,146,035. In said disclosure it has i.a. been indicated that in a process for the isomerisation of butenes use can be made of a catalyst comprising a metal aluminophosphate as described in general terms in US 4,567,029. Surprisingly, it has now been found that an improved yield of branched olefins can be obtained if a hydrocarbonaceous feedstock comprising linear olefins having at least four carbon atoms is contacted with a catalyst comprising a medium-pore molecular sieve selected from a specific group of MeAPO and MeAPSO medium-pore molecular sieves. Accordingly, the present invention relates to a process for the preparation of branched olefins comprising contacting a hydrocarbonaceous feedstock comprising linear olefins having at least four carbon atoms at elevated temperature with a catalyst which comprises a MeAPO and/or MeAPSO medium-pore molecular sieve having an anhydrous composition expressed in molar oxide ratios as follows; (MeO) a (Al 2 O 3 ) b (P 2 O 5 ) c (SiO 2 ) d , whereby (a + b)/c is greater than 1.0, a ranges from 0.003 to 0.2, b and c range from 0.05 to 0.3, d is at most 0.4 and a/(c + d) is at least 0.05 when SiO 2 is present, and Me is at least one of Mg, Mn, Co and Zn. In this way a very attractive high yield of branched olefins can be obtained. In the context of the present invention a MeAPO medium-pore molecular sieve is defined as a crystalline microporous metal aluminophosphate composition having a three-dimensional framework structure of interconnected MeO 2 , AlO 2 and PO 2 tetrahedral units. This type of medium-pore molecular sieve and its preparation have for instance been described in US 4,567,029 which is hereby incorporated by reference. Further, in the context of the present invention a MeAPSO medium-pore molecular sieve is defined as a crystalline microporous metal silicoaluminophosphate having a three-dimensional framework structure of interconnected MeO 2 , AlO 2 , SiO 2 and PO 2 tetrahedral units. MeAPSO medium-pore molecular sieves and their preparation have for example been disclosed in EP 158348, EP 158975, EP 161489 and EP 161490 which are hereby incorporated by reference. Preferably, in the process according to the present invention use is made of a MeAPO and/or MeAPSO medium-pore molecular sieve having an anhydrous composition expressed in molar oxide ratios as follows: (MeO) a (Al 2 O 3 ) b (P 2 O 5 ) c (SiO 2 ) d , wherein a ranges from preferably from 0.01 to 0.15, b ranges from 0.05 to 0.25, c ranges from 0.05 to 0.25 and d is at most 0.3. Preferably, the hydrocarbonaceous feedstock comprising linear olefins having at least four carbon atoms is contacted with a catalyst comprising a MeAPO and/or MeAPSO medium-pore molecular sieve, wherein Me is at least Co. Suitable MeAP(S)O catalysts include catalysts identified by the IUPAC Commission on zeolite nomenclature as AEL (CoAP(s)O-11), AFO, AFR, AFS, AFY, ATN and ATO. Preferred MeAP(S)O catalysts include CoAPO-11 type catalysts. In the context of the present invention a medium-pore molecular sieve is defined as having an average pore diameter in the range of 3.8 to 7 Å, preferably in the range of 4 to 6.5 Å. The catalyst to be used in the process according to the present invention may comprise one or more MeAPO and/or one or more MeAPSO medium-pore molecular sieves as defined hereinabove. The catalyst may comprise in addition to the MeAPO and/or MeAPSO medium-pore molecular sieve a porous matrix material. Suitable porous matrix materials include, for instance, silica, alumina, zirconia and titania and mixtures thereof. When SiO 2 is present in the medium-pore molecular sieve to be applied in the present process, a/(c + d) is preferably at least 0.08. Suitably, use is made in the present process of a medium-pore molecular sieve as described hereinbefore, wherein (a + b)/c is at most 3. Suitably, use is made in the present process of a medium-pore molecular sieve as described hereinbefore, wherein a/(c + d) is at most 2. The hydrocarbonaceous feedstock to be converted in accordance with the present invention comprises linear olefins having at least four carbon atoms. In the context of the present invention, the hydrocarbonaceous feedstock may either comprise two or more types of linear olefins having at least four carbon atoms or may comprise only one specific type of linear olefin having at least four carbon atoms. Suitably, the feedstock comprises linear olefins having four to ten carbon atoms. Preferably, the feedstock comprises linear olefins having four to six carbon atoms. More preferably, the feedstock comprises n-butene(s) and/or n-pentene(s). Suitably, the feedstock comprises at least 50 %wt n-butene(s) and/or n-pentene(s). Suitably, the feedstock consists essentially of n-butene(s). Suitably, the hydrocarbonaceous feedstock to be converted has been obtained from a steam cracking and/or catalytic cracking process. Process conditions which can suitably be applied, comprise a temperature of 200 to 480 °C and an olefin partial pressure of at least 0.5 bar and a total pressure of between 0.5 and 25 bar. Preferred conditions comprise a temperature of 300 to 450 °C and an olefin partial pressure of at least 0.7 bar. Suitably, unconverted linear olefins are separated from branched olefins downstream the reaction zone wherein the isomerisation process is carried out, and recycled to the reaction zone. Such a separation can suitably be carried out by means of a molecular sieve. The invention will now be illustrated by means of the following Examples. Example 1 (according to the invention) Catalyst preparation. Cobalt (II) acetate tetrahydrate dissolved in water was combined with aluminium isopropoxide and homogenized until a gel was obtained. A second solution, consisting of orthophosphoric acid and water, and subsequently di-n-propylamine were added under agitation. The composition of the final reaction gel expressed in molar (oxide) ratios was as follows: 0.17 CoO : 1 Al 2 O 3 : 1 P 2 O 5 : 1 R : 45 H 2 O, wherein R is di-n-propylamine. The reaction gel was then transferred to an autoclave to crystallize at 160 °C for 48 hours. The solid material obtained was subsequently recovered by filtration, washed with water and dried in air at 120 °C. Thereafter, the solid material was calcined in air at 550 °C for 3 hours. The product obtained had an X-ray diffraction pattern characteristic of highly crystalline CoAPO-11, and its anhydrous composition expressed in molar ratios was as follows: (CoO) 0.047 (Al 2 O 3 ) 0.27 (P 2 O 2 ) 0.25 . Subsequently, the CoAPO-11 powder obtained was pressed, crushed and sieved in order to obtain a 40-80 mesh fraction of pellets of a catalyst A. Example 2 (according to the invention) Catalyst preparation. A catalyst B was prepared in the same way as catalyst A, except that the final reaction gel had a composition in molar (oxide) ratios as follows: 0.1 CoO : 1 Al 2 O 3 : 1 P 2 O 5 : 1 R : 45 H 2 O, and the product obtained after calcination in air at 550 °C for 3 hours had the following anhydrous composition expressed in molar oxide ratios: (CoO) 0.024 (Al 2 O 3 ) 0.25 (P 2 O 5 ) 0.25 . Example 3 (not according to the invention) Catalyst preparation. A catalyst C was prepared in the same way as catalysts A and B, except that the final reaction gel had a composition in molar (oxide) ratios as follows: 0.05 CoO : 1 Al 2 O 3 : 1 P 2 O 5 : 1 R : 45 H 2 O, and the product obtained after calcination in air at 550 °C for 3 hours had the following anhydrous composition expressed in molar oxide ratios: (CoO) 0.009 (Al 2 O 3 ) 0.24 (P 2 O 5 ) 0.25 . Example 4 Experiments. Each of the catalysts A-C was contacted in the presence of argon with a feedstock consisting of 1-butene at a temperature of 350 °C, an olefin partial pressure of 1 bar, a total pressure of 4 bar, and a weight hourly space velocity of 2 kg/ (kg.h). The products obtained after 45 hours (catalysts A and C) or 46 hours (catalyst B) on stream are shown in Table 1 hereinbelow. Catalyst composition: A B C (a + b)/c 1.3 1.1 1.0 Product (% by weight): ethene 0.11 propane 0.11 0.28 propene 0.8 1.98 3.53 butane 0.95 1.52 2.20 n-butene 41.51 31.52 27.24 iso-butene 37.89 30.85 26.65 C 5 + liquids 18.85 34.02 39.99 It will be clear from the above that processes which are carried out in accordance with the present invention (use of catalysts A and B) are much more attractive in terms of iso-butene production than a process just falling outside the scope of the present invention (use of catalyst C).

Claims: Process for the preparation of branched olefins comprising contacting a hydrocarbonaceous feedstock comprising linear olefins having at least four carbon atoms at elevated temperature with a catalyst which comprises a MeAPO and/or MeAPSO medium-pore molecular sieve having an anhydrous composition expressed in molar oxide ratios as follows; (MeO) a (Al 2 O 3 ) b (P 2 O 5 ) c (SiO 2 ) d , whereby (a + b)/c is greater than 1.0, a ranges from 0.003 to 0.2, b and c range from 0.05 to 0.3, d is at most 0.4 and a/(c + d) is at least 0.05 when SiO 2 is present, and Me is at least one of Mg, Mn, Co and Zn. Process according to claim 1, wherein a ranges from 0.01 to 0.15, b and c range from 0.05 to 0.25, and d is at most 0.3 when SiO 2 is present. Process according to claim 1 or 2, wherein Me is at least Co. Process according to any one of claims 1-3, wherein a/(c + d) is at least 0.08 when SiO 2 is present. Process according to any one of claims 1-4, wherein the hydrocarbonaceous feedstock comprises at least 50 %wt n-butene(s) and/or n-pentene(s). Process according to any one of claims 1-5, wherein the process is carried out at a temperature of 250 to 480 °C, an olefin partial pressure of at least 0.5 bar and a total pressure of between 0.5 and 25 bar.

Inventors: JONGKIND HERMANUS, KRAUSHAAR-CZARNETZKI BETTINA, JONGKIND, HERMANUS, KRAUSHAAR-CZARNETZKI, BETTINA
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1994
Main classification: C07C5
IPC codes: B01J29, C07C5